Method and apparatus for the removal or recovery of vapors from air



March 3, 1959 R. T. PRING 2,875,844

METHOD AND APPARATUS FOR THE REMOVAL. 0R

RECOVERY oF vAPoRs FROM AIR Filed March 21, 1957 l vso 32 ao i J6- T 22 ELSRIRx-J flg'g'll ET- g. l

INVENTOR. ROBERT T. PRN;

United States Patent O j 2,875,844 Ice Patented Mans, 1959.

kMETHOD AND APPARATUS FOR THE REMOVAL OR RECOVERY OF VAPORS FROM AIR Application March 21, 1957, Serial No. 647,644 13 Claims. (Cl. ISB-4.3)

This invention relates to the processing of air or other gaseous medium to remove contaminating or other vapors present in the air, and it relates more particularly to a method and apparatus for electively removing vapors from air or other gaseous medium for purification of the air or other gaseous medium or for recovery of the vapor which is present in the air or other gaseous medium.

It is van object of this invention to provide a new and improved means and method for the removal or recovery of vapors from air or other gaseous medium, and it is a related object to provide a method and means of 'the type described which is substantiallyfree of the limitations characterizing vaporremoval processes and equipment heretofore employed and which `is effective for removal of vapors even when present in low concentrations'as well as in high concentrations in the air or other gaseous medium.

These and other objects and advantages of this invention will hereinafter be set forth and for purposes' of illustration, but not of limitation, an embodiment of the invention is shown in the accompanying drawing, in Which Figurel is a pictorial ow sheet of a system embodying the features of this invention; and Figure 2 is a sectional view through a filter unit employed in the practice of this invention. f

2. the bed as the first portions progressively become satisfied or saturated in use.

The adsorption process is exothermic in that heat is given oi. Because of the static character of the beds, dissipation of heat 'which is generated becomes necessary, otherwisea reversal of the adsorption reaction becomes possible. Some systems provide for the addition of water vapor to the air forced through the bed for temperature control, while others wet the activated carbonaceous material. Either is undesirable' because of the interferences which are established with the normal adsorption process and the ability to make maximum use of the adsorption material. j

Because of the static nature of the packed beds of activated carbonaceous material, when the beds become Vl somewhat saturated to the extent thatv they are incapable of removal of the desired amounts of vapor from the air, as when the bed reaches the break throng point, it becomes necessary to replace the activated carbonaceous material. Regeneration, as by removal of the spent adsorbent and repacking of the tower with the activated carbonaceous material, represents a time-consuming and laborious operation which makes it necessary to provide for a duplicate set of equipment so as to have one available for placement into the system lwhile the other is being repacked for use. rBecause of the relatively high cost of packed towers and because of the necessity for duplication of equipment, systems which make use of towers packed with activated carbonaceous material have been impractical from the standpoint of cost as well as v efficiency.

Since, in most instances, thefatmosphere treated will consist of air contaminated with the vapors to-be removed, the specification and claims will hereinafter referv to air as representative of the gaseous medium. It will be understood, however, that other gasessuch as oxygen, nitrogen and the like may be included.v

To the present, use has been made commercially of adsorption systems for the removal of certain vapors from air wherein activated carbonaceous materials have been employed as the adsorptive medium'. Such activated carbonaceous materials, in the form of relatively large or coarse particles, have been formed into reactor beds in packed columns or towers through which 'the air is passed to bring the vapors into contacting relation with the activated carbonaceous material for removal from the air by adsorption. e

Columns packed with beds 'material have been used quite successfully for the removal of contaminating vapors from air. `The principal objection to their use stems from the static character of the system which limits its application and use. In adsorption towers, one or more beds are packed with the 'relatively large particles of the activatedy carbonaceous material. The contaminated air is forced throughl the packed column. The contaminating vapor or gas is ad- `lsorbed almost immediately upon engagement with the adsorbent surface of the activated carbonaceous material 'so that adsorption is rapid at lirst but then slows down as thesurface portions of the activated carbonaceous I material become satisfied or saturated with the vapor.

In' addition, the adsorbing action progresses from the 1arca of the bed Nfirst contacted to 'the point of exit from Vthe air through the beds.

Further, packed adsorption towers of the types heretofore employed have been restricted in their use tothe treatment of relatively small amounts of air or other gaseous material. Large amounts of air cannot eiiiciently be processed through packed towers because of the large pressure drop which occurs across the packing. 4This necessitates the use of large amounts of power to lforce This lvolumetric limitation imposes a restriction with respect to the ability to make elfective and eiicient -use of packed towers where Vthe vvapor to be removed is present in theair in low concentrations or wherein large amounts of air or other gaseous media are to be treated.k Thus, packed towersl are incapable of practical use in the treatmentA of exhausts lfrom processing equipment where the vapors might be present .inl the exhaust in concentrations as low as parts per million or even 400 parts per million.

A further objectionable feature in the use of packed `columns .as a dry scrubber for the removal of vapors falls off rapidly to the extent that it becomes necessary to take the tower off stream forregeneration of :the

adsorbent.

These same objectionable characteristics are to be found also in lluid bed'reactors wherein the carbonaceous 'materials in the bed are agitated by the entering contaminatedgas stream so'that the aerated mass has a tendency to behave more as a fluid. As in the` static beds of packed columns, the carbonaceous particles remain in place. These fluid'type reactor beds share the disadvantages of packed towers from the standpoint at least of high pressure loss, expense of equipment` and the necessity vto duplicate the equipment to permit regeneration.

It has been found that vapors can be effectively and efficiently removed from air when present in concentrations greater than 500,000Hpartsper million or when present inv such lowv concentrations as `75 parts per million by the combination ofr steps which includes 1) the introduction f-activatedcarbonaceous material or other solid adsorbent in finely divided form into the air-stream for direct dispersion into the air stream contaminated-with the vapors-to be removed, and (2) the passage of thecontarninated air stream, containing the dispersed particles of adsorbent material, through a iilter surface on. bwhich the particles of adsorbent -are separatedfrorn the air to form a permeable layer through which oncoming air'must pass before being exhausted to the atmosphere, thereby to bring the vapors remaining linl the'air into -intimate contacting relation with freshly deposited, unsaturated, or partially unsaturated adsorbent capable of efficient removal of vapor from the air stream.

TheA activated carbonaceous material dispersed as line particles-in the air provides a fluid system capable of bringing the linely divided adsorbent particles into intimate contacting relation with the vapors that are to befremoved'from the air. Becausev the iinely divided particles; of carbonaceous material dispersed in the air provide a tremendousamount of surface area per unit weight by-lcomparison .with the coarse particles of carbonaceous material in thev static beds of the contact towers, thegreatest proportionr of the vapors to be lremoved 4from the air will be taken up by adsorption almost immediately while the activated adsorbent is still dispersed as fine particles in the air. The remainder, or at least substantial portions of the remainder of the vapors in the air, will be-removedby the subsequent lintimate contacting relation. between the vapors and the activated carbonaceous` or other adsorbent material as the air `is caused -tofllter-throughthe porous and perjrneable layer of iinely divided adsorbent-lining of the filter fabric. Bythe combination of steps described, betterthan 95% Vand more often 100% removal can be veiectedwithless power consumption and with negligible `pressure drop byy comparison with the pressure drop `experienced throughthe static layers 'of coarse particles 'offcarbonaceous material'employed in packed towers. Thusthe process embodying the features of this inventionis applicable tothe treatment of such large volumes oflairfaswould-#be--irnpracticable with packed towers and-'forme Aremovalvof contaminating vapors present in such low concentrations as would be incapable of effective treatment with packed towers.

In the practice of this'inventiom activated carbonaceous 'or-other adsorbent material is-continuously introduced into theair in an amount in excess of that capable "of being saturated by theY amount ofv removable contaminating vapors present in the air. Itis preferred 'to make-use of a Isubstantial excess of the adsorbent, such VYasian amount greater than two times the weight of the adsorbing reagent capable `of being saturated by the -lcontaminating vapors and preferably in an amount ywhich is from four to ten times greater than the amount capable of being satised by the contaminating vapors present 'inthe air.

; '.Any gas onvapor capable of being adsorbed in conventional beds of activated charcoal can 4be `removed from air or other gaseous media by the process described. YThisincludes almost any organic compound which can exist at normal temperature in a gaseous or vapor phase. Where the adsorbent is to be reactivated for use, or when the vapor is to be recovered, use can be made of the described process to recover vapors which, under the conditions existing in the regeneration or recovery,

.do not break down to form a relatively non-volatile solid `having viscous or adhesive properties. Solvent vapors,

whether aliphatic, cyclic or heterocyclic, can be removed, including alcohols, ethers, aldehydes, ketones, esters, and certain organo-metallic compounds and derivatives thereof. The process described` can be used eiiectively to remove organic compounds that produce objectionable odors, such as mercaptans, gaseous or vapor phase decomposition products ofv animal or vegetable origin; halogenated hydrocarbons; hydrides or oxides of certain inorganic compoundsand metals including hydrogen sulde, phosphine, sulphur dioxide and the like. It will be understood that the eiiiciency of adsorption will vary somewhat inversely with the molecular weight of the particular material in a given class. Thus, high boiling organic substances may be more readily adsorbed than some of the low boiling materials or derivatives.

As the adsorbent material, it is preferred to make use of activated carbonaceous materials, as represented by activated charcoal from wood products, activated carbon from coal or petroleum products, or other conventional adsorbent activated carbonaceous material. Though not equivalent, use can also be made of activated alumina and silica gel as the iinely divided adsorbent particles dispersed in the air stream for remvoal of vapors, both organic and inorganic. For example, activated alumina is effective .in the removal of inorganic gaseous compounds such as sulphur dioxide and the like. For dispersion in the .air stream, itis desirable to make use of adsorbentmaterial reduced to a particle size capable of being suspended in and` conveyed by the flowing gaseous or air stream. In practice, use can be made of activated carbonaceous or other adsorbent material reduced to a particle size ywhich is minus 200 mesh and preferably minus 200 and plus 325 mesh.

With reference to the dispersion of the finely divided particles of adsorbent material inair, itwill be apparent thatheat generation, which represents a problem ofdissipation in the static beds in packed columns, will not present a barrier to the use of a iiuid system of the type described because the dilution of the finely divided particles of adsorbent material, separately dispersed in the air, will enable heat of adsorption to become immediately dissipated into the air stream to be carried away by the air. Thus, without the -static heat-insulating characteristics of the packed column, temperature build-up is incapable offtaking place where admixture of thetype described exists or where heat of adsorption takes place while `the particles are separately dispersed in the air and where large vvolumes of air are present by comparison with the amount of adsorbent material.

Another important factor in the improvement of the adsorption process by the system described resides inthe relatively large amount of surface area available per volume of weight of the iinely divided adsorbent material, as distinguished from the considerably smaller amount of surface area available in an equivalent weight of adsorbent material employed in static systems characteristic of packed towers or reactor beds. As a result, the amount of adsorbent material for removal of an equivalent amount of vapor from the air is considerably less in the system described as compared with the packed towers or reactor beds heretofore employed. Similarly, maximum use can be made of the finely divided materials as an adsorbent whereby more eicient use can be made of the adsorbent materials employed in the system described herein.

A further important concept resides in the greater exibility which. characterizes the process formingthe subject matter of this invention. With reference to the systems which make. useof static beds of adsorbentmaterial, adsorption at a relatively high rate remains constant until the adsorbent material forming the bed be'- comes saturated with the vapors extracted. When saturation or break through is reached, the eiiiciency of the unit falls orf materially to the extent that the tower or bed becoine's` unt for further use. At this point, the tower is taken ot stream for regeneration of the adsorbent.

A similar break through point will not be reached in the process forming the subject matter of this invention because an amount of finely divided adsorbent material is continuously being introduced into the air which is in excess of the amount required for adsorbing all of the vapors available in the air, and preferably more than twice the amount capable of being saturated by the amount of vapor in thel air. As a result, a saturation point similar to that reached in the static systems heretofore employed is avoided and maximum adsorption eiciency is constantly maintained throughout the cycle. An important concept of this invention resides in the fact that only a shallow deposit of adsorbing material is required on the lter surface because the exposed por-y tions are always in an active state and are constantly being replaced by fresh or partially saturated adsorbing material especially when coupled with the condition whereby much of the adsorption has already occurred in earlier parts of the ue system.

With reference to the finely divided adsorbent which is filtered from the air stream to form the porous layer through which the contaminated air is filtered, the characteristics of the thin permeable layer of finely divided adsorbent materials built up on the surface of the lter fabric provide very little resistance to gaseous flow whereby pressure drop through the ilter system is insignificant by comparison with the pressure drop that takes place when an equivalent amount of contaminated air is processed through a packed column of adsorbent material. In a system embodying the practice of this invention, a pressure drop of 7 inches of water is usually themaximum which will be experienced in the treatment of air as compared to a pressuredrop of 20 inches ot mercury secured in the treatment of air at an equivalent rate in a packed column.

' Because of the nely divided character of the adsorbent material, the layer that is formed is highly permeable and offers little resistance to the ow of air therethrough. Inw general, it is preferred to operate the system until a thickness suicient to cause excessive pressure drop' is reached. With some systems such conditions may be v reached at about 1/2 inch. Because the amount of adsorbent material introduced initially into the air is more than enough to satisfy the vapors in the air, and because such nely divided adsorbent material is constantly being deposited to form ya part of the built-up porous layer in the same ratio described as between the adsorbent and the vapors in the air, the permeable layer that is formed is always capable of extracting vapors from the system to the end that a break through point, characteristic of packed towers, will be incapable of being reached inthe system described.

- Referring now to the pictorial representation of the ow of materials, the numeral 10 represents a receptacle it is preferred to make use of a bag type lter having a high proportion of filter surface area, such as is described in the issued Patents No. 2,137,254 and No. 2,143,664. The filter device, illustrated by the numeral 16, is formed with an inlet plenum chamberr 22 having an inlet at one end through which the contaminated air is introduced from the passage 14. The top wall of the inlet plenum chamber is formed with a plurality of openings 32 in communication with the ends at the bottom of a plurality of lter tubes 18 formed of a filter fabric 26. The tubes 18 are closed at the top 34 and suspended from hanger rods 35. The latter are connected for rocking movement onto a shaker bar 20 for agitation of the bags to loosen particulate substances collected as a layer 24 on the inner walls thereof. Thus, the collected material is removed from the walls of the filter tubes when the thickness ofthe layer 24 becomes excessive to cause containing particulate adsorbent material 11 adapted to be introduced at a desired rate into a passage 14 through which the contaminated air 12 is caused to flow from a piece of process equipment to a filtration device 16. The particulate adsorbent 11 is introduced into the passage 14 in the desired amount for dispersion with the contaminated air stream. In general, uniform dispersion occurs automatically at air velocities sucient for conveyance. If desired, additional means may be embodied within the passage for causing turbulent ow to enhance the dispersion or for maintaining the dispersed phase, or a dispersion chamber or other means may be employed for effecting uniform distribution of the adsorbent particles 11 in the contaminated air 12 during the remainder of travel with the air through the passage 14 to the filtration device.

Use can be made of any conventional filtration device having a porous filter surface Vthrough which the volume of. air; canA iiow` without noticeableV pressure drop rbutnoticeable increase in the pressure drop across the lter section. Agitation of the filter tubes for removal is effected while the air flow is cut off to permit the dry particulate substances to fall gravitationally downwardly through the inlet plenum chamber 22 to a collecting -hopper -28 where the particulate material is gathered for further processing as by treatment to recover the vapor or to regenerate the adsorbent material, or both. Instead, the adsorbent can be cleaned from the surfaces of the filter tubes by a reverse jet principle, i. e. by reversing the ilow of air through the tubes. The lter tubes are preferably arranged in separated compartments for enabling continuous and automatic operation with but a single unit, ow taking place through the tubes in only The lter tubes 18 are preferably formed of conven-I tional textile materials, such as cotton, but they may also be formed of synthetic iibers of organic polymeric materials, or glass, having higher strength than natural iibers and more resistance to the vapors which might be brought into contact therewith. In addition, such synthetic fibers can be employed where it is desirable to have `a higher degree of thermostability, thereby to enable use of the device in the treatment of contaminated air at elevated temperature. v

When the accumulation of adsorbent particles on the ingoing side of the lter fabric is such as to cause excessive pressure drop during passage of the air across the composite layers, the operation of one portion of the filter can be stopped to shake down the tubes while operation continues in another portion of the multiple coml partment filter unit. When such means are provided;

for sequential operation of portions of the filter device, for cleaning one portion when another is in operation, a system for the continuous treatment of air for the removal of contaminating vapors and gasesy is provided.

It will be apparent further, by way of still another advantage,`thatyremoval of the vapor from the air or other `gaseous medium can be caused to take placeeficiently and electively without the pressure drops characteristic of packed towers or reactor beds. Thus, the power requirements for a system embodying the features of rthis invention will 4be much less than those which are required for the static systems heretofore employed. As a result, considerably larger volumes of air or other gaseous medium can be economically treated in a continuous operation, thereby to permit the process described to be used in commercial applications where the amount of contaminant may represent a small proportion, such as less than parts per million of the air by weight.

The spent adsorbent material removed from the lter -tubes canbe regenerated by a batch process of treatnated andthe regenerated 'adsorbent material either'cooledY or driedfor return in a continuous'cycle for redispersionvr inthe contaminated air-. Regeneration can be accom-- plished by exposing the yadsorbent to steam, vas by passing w'et steamV througliwthe 'spent'.l adsorbent, or it can be regeneratedby heating the adsorbent to an elevated temperature while making use of a slow stream of air or inert gas to carry away the released organic vapors.

Where the organic vapors removed are of Aeconomic: value or otherwise useful, the concentration of the organic vapors released or themanner in whichthe organic vapors arel released can be selectively controlled to permit economical recovery. Where recovery is impractical or uneconomi'cal, the organic vapors can be destroyed by combusition, catalytic combustion or other means. Processe`s for the recovery of solvent vapors and other organic vapors from spent adsorbent are well known. These include the processes of condensation, Water scrubbing, or adsorption by scrubbing `with compatible liquids.

B'y'way of illustration, in the removal of xylene vapors present in a concentration averaging about 440 parts per million, the contaminated air was treated by introducing activated carbon (plus 325 mesh-minus 200 mesh) into the air stream in a concentration of about 30 pounds of` carbon per l pound of Xylene vapors contained in the air. The activiated carbon was introduced into the contaminated air stream 12 during travel through the passage 14 for dispersion of the particles with the air. The contaminated air with the dispersed particles of activated carbon was then filtered through a bag house filter 16` having an air-to-cloth ratio of 3.7 cubic feet of air per minute to l square foot of filter surface. The bag house was operated on a 71/2 minute cycle with 1/2 minute between shake-downs.

In operation, a pressure increase of 11/2 inch water gauge was securedacross the composite filter layers and practicallyv 100% removal of the Xylene vapors was effe'ct'ed. They dispersion of adsorbent particles in the air wa'smaintained for less than ly second before the con tarninated air entered the bag house.

In' another operation, air containing 765 parts per million of solvent vapors was treated in substantially the same manner with activated carbon of the described mesh size introduced into the contaminated air in amounts of about 11 pounds per pound of solvent vapors contained in the air. The contaminated air was passed through the filter'surface at the rate of 4.2 cubic feet per minute per square foot of filter cloth. A pressure increase in the range of 1.7'inch water gauge was secured with better tha`n85% removal of vapors. The treatment of an equivalent amount of air through a packed tower for equivalent removal would have caused a pressure increase inthe order of 22 inches of water through the reactor bed. In the practice of this invention, the bag house was divided into two compartments, each one alternately operating on a 71/2 minute cycle with 71/2 minutes shutdown' between cycles, of which 38 seconds was consumed irrshakingy the filter bags.

It willy be apparent from the foregoing that I have provided a-new and improved process for the removal or recovery of vapors present as a contaminant in air or other gaseous medium in low as well as in high concentration.,` such as in concentrations ranging from less than 70 'or less than 440 p. p. rn. to as high as 50,000 p. p. m. The described process is free of most of the objectionable features present in static vapor removal systems which have heretofore been employed, and the process described is capable of use'in a continuous operation for removal o f'vapors from air or other gaseous medium issuing constantly and'at a relatively uniform rate from devices and reactions employed in the process industries. The process described further provides for continuous operation in regeneration of the adsorbent for return to the removal cycle.

In the description of the process reference has been made to air` as the medium contaminated by the organic vapors.A It will be understood that the-termair, will Cil , gaseous stream, and then passing the gaseous stream with the particulate substance distributed therein through a porous layer built upV of the nely divided adsorbentl material whereby the dispersed particles of adsorbentl material having contaminating vaporsl adsorbed thereonA are tiltered out of the gaseous stream to form a part of the porous layer through whichl the gaseous stream must flow inL intimate contact to enable removal of additional" amounts of contaminating vapors therefrom.

2. In the method of removing contaminating organic vapors from air, the steps of introducing an activated? carbonaceous material in nely divided form into the lcontaminated air stream and dispersing the particulate adsorbent material therein whereby some of the contami-v nating vapors are adsorbed by the particulate adsorbent dispersed in the air stream, and then passing the gaseous stream with the particulate adsorbent distributed thereinj through a permeable layer built up of the finely divided adsorbent whereby the dispersedy particles of adsorbent having contaminating vapors adsorbed therein from the contaminated air during travel therewith are filtered out of the `air stream to form a part of the porous layer through which ysubsequent portions of the air stream must flow in intimate contact to enable removal of additional amounts of contaminating vapors therefrom.

3. The method as claimed in claim l in which the dry particulate substance is dimensioned to have a particle size less than 200 mesh.

4. The method as claimed in claim l in which the dry particulate substance is introduced into the gaseous stream in an amount not less than that theoretically required to adsorb the contaminating vapors in the air stream.

5. The method as claimed in claim 4 in which the particulate substance is introduced into the air in an.

amount at least twice the theoretical amount.

6. The method as claimed in claim l which includesV the additional steps of stopping the flow of contaminated gaseous medium through the built up layer on the. filter surface at intervals when the built up layer of particulate surface of the filter for subsequent flow.

7. Means for the removal of organic vapors present as a contaminant in a gaseous medium comprising a housinghaving an inlet at one end and an outlet at another, lter elements within the housing arranged in the path of gaseous medium passing therethrough so as to cause the gaseous medium to pass through the filter elements when traveling from the inlet to the outlet, a passage in communication with the inlet to the housing `for introducing the gaseous medium contaminated with the organic vapors into the housing, means for causing the gaseous medium to travel through the passage in turbulent ow' to the inlet of the housing, means for introducing-a dry particulate adsorbent material into the passageA for suspension in the contaminated gaseous mediumduring.y

travel through the passage whereby the particulate sub`- stance' becomes suspended in the gaseous stream for the removal of organic vapors coming in surface contact therewithsaid means being characterized by thefact that' the particulate adsorbent material suspended in the gaseous 1 medium becomes separated on the ingoing side of the filter element to form a permeable layer through which the contaminated gaseous medium must pass in intimate contacting relation, and means for intermittently removing the layer of particulate substance built up on the ingoing side of the filter element.

8. Means as claimed in claim 7 which includes the built up layer of adsorbent particles on the ingoing side of the lter element and in which the built up layer is of a thickness less than that to cause excessive pressure drop during passage of the gaseous medium thereacross.

9. Means as claimed in claim 7 in which the adsorbent material comprises an activated carbonaceous material.

10. Means as claimed in claim 9 in which the activated carbonaceous material is of a particle size of minus 200 to plus 325vmesh.

11. Means as claimed in claim 7 in which. the lter element comprises a plurality of elongate filter tubes and in which the means for removing the layer of particulate substance collected on the ingoing side of the lter tubes comprises means for agitating the tubes with the gaseous stream cut oir.

12. In the method of removing contaminating vapors from a gaseous system, the steps of introducing an active adsorbent material in inely divided form into the gaseous stream containing the contaminating vapors and dispersing the particulate adsorbent into the contaminated gaseous stream whereby the particulate adsorbent re moves some of the contaminating vapors from the gaseous stream while dispersed therein and then passing the gaseous stream with the particulate substance dispersed therein through a porous layer built up of the nely divided adsorbent material whereby dispersed particles of the adsorbent material having contaminating vapors adsorbed therein are filtered out of the gaseous stream to form the outermost portions of the porous layer through which the gaseous stream must ow in intimate contact to enable additional removal of contaminating vapors therefrom, reversing the ow of the gaseous stream through the iilter elements to remove spent adsorbent present in the formed layer, and then continuing the cycle as previously dened.

13. Means for the removal of organic vapors present as a contaminant in a gaseous medium as claimed in claim 7 in which the filter elements in the housing are divided in separate compartments some of which are on stream While others are ot stream for regeneration so as to enable use of the filter housing in a continuous operation.

References Cited in the le of this patent UNITED STATES PATENTS 1,366,655 Haslup Jan. 25, 1921 2,411,208 Hall et al. Nov. 19, 1946 2,492,401 Schutte Dec. 27, 1949 2,747,681- Schuftan et al. May 29, 1956 

